CA2502329C - Method and system for inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel - Google Patents
Method and system for inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel Download PDFInfo
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- CA2502329C CA2502329C CA2502329A CA2502329A CA2502329C CA 2502329 C CA2502329 C CA 2502329C CA 2502329 A CA2502329 A CA 2502329A CA 2502329 A CA2502329 A CA 2502329A CA 2502329 C CA2502329 C CA 2502329C
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000000926 separation method Methods 0.000 title claims abstract description 35
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 57
- 239000002904 solvent Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002347 injection Methods 0.000 claims abstract description 30
- 239000007924 injection Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 6
- 229920000620 organic polymer Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
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- 230000000712 assembly Effects 0.000 abstract 1
- 238000000429 assembly Methods 0.000 abstract 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003027 oil sand Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 230000010411 postconditioning Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/045—Separation of insoluble materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/047—Hot water or cold water extraction processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Degasification And Air Bubble Elimination (AREA)
Abstract
The present invention relates to a method of inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel. Diluted bitumen froth is separated in the vessel into a low density fraction comprising bitumen and a solvent and a high density fraction, comprising solid particles, water and asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water. A water-asphaltene dispersant is added to the froth prior to adding solvent. The invention also comprises a system, wherein bitumen is delivered to a bitumen froth separation vessel via a froth supply conduit comprising a first injection assembly for injecting the water-asphaltene dispersant, and a second injection assembly for injecting the solvent. The first and second injection assemblies are longitudinally spaced at a distance along the conduit, with the first injection assembly located upstream of the second injection assembly.
Description
METHOD AND SYSTEM FOR INHIBITING DEWATERING OF ASPHALTENE
FLOCS IN A BITUMEN FROTH SEPARATION VESSEL
The present invention relates to a method and system for inhibiting dewatering of asphaltenes in a process for recovery of bitumen from oil sand.
BACKGROUND OF THE INVENTION
In a typical oil sand processing plant, mined oil sand is mixed with water to produce a slurry. The slurry is an emulsion of bitumen (a heavy liquid hydrocarbon) and other components of the sand in water. The slurry is screened to remove oversize rocks and oil sand lumps and then conditioned in a hydrotransport pipeline or via other conditioning means. The thus conditioned slurry is introduced into a slurry separation vessel from which a bitumen froth is recovered. The froth may then be treated, such as by adding a paraffinic or other solvent and/or other agents, to promote the separation of bitumen from the other components of the froth, including water, solvent or other agents, and residual solids.
A number of different froth treatment processes have been described. For example, in Canadian patent No. 2,149,737, a process is described wherein a bitumen froth is mixed with a paraffinic solvent and fed to a primary bitumen froth separation vessel. In the froth, the bitumen forms an emulsion with water. Mixing the froth with the paraffinic solvent initiates a transformation resulting in the formation of bitumen globules that separate from the water and rise to the top of the bitumen froth separation vessel to form a bitumen froth upper layer. Bitumen is subsequently withdrawn from the overflow of the vessel and further treated.
FLOCS IN A BITUMEN FROTH SEPARATION VESSEL
The present invention relates to a method and system for inhibiting dewatering of asphaltenes in a process for recovery of bitumen from oil sand.
BACKGROUND OF THE INVENTION
In a typical oil sand processing plant, mined oil sand is mixed with water to produce a slurry. The slurry is an emulsion of bitumen (a heavy liquid hydrocarbon) and other components of the sand in water. The slurry is screened to remove oversize rocks and oil sand lumps and then conditioned in a hydrotransport pipeline or via other conditioning means. The thus conditioned slurry is introduced into a slurry separation vessel from which a bitumen froth is recovered. The froth may then be treated, such as by adding a paraffinic or other solvent and/or other agents, to promote the separation of bitumen from the other components of the froth, including water, solvent or other agents, and residual solids.
A number of different froth treatment processes have been described. For example, in Canadian patent No. 2,149,737, a process is described wherein a bitumen froth is mixed with a paraffinic solvent and fed to a primary bitumen froth separation vessel. In the froth, the bitumen forms an emulsion with water. Mixing the froth with the paraffinic solvent initiates a transformation resulting in the formation of bitumen globules that separate from the water and rise to the top of the bitumen froth separation vessel to form a bitumen froth upper layer. Bitumen is subsequently withdrawn from the overflow of the vessel and further treated.
2 The other components of the mixture form a dense fluid underflow comprising: water; solids (including clays);
and a hydrocarbon emulsion comprising water and residual bitumen enriched in asphaltenes. The underflow is withdrawn from the bottom of the primary separation vessel. The underflow is then usually further treated in secondary and subsequent separation vessels to recover residual bitumen.
The underflow from the paraffinic froth treatment process described above may also be treated to form agglomerates of asphaltenes and clays that may then be withdrawn as a separate product stream, as described in Canadian patent No. 2,232,929.
One problem with current conditioning processes is that precipitated asphaltenes in the underflow of bitumen froth separation vessels agglomerate, which agglomerates can form solid masses that can interfere with processing equipment.
For instance, in the paraffinic froth treatment process, the underflow separates over time into a water and hydrocarbon phase. The water phase comprises free water and mineral solids. The hydrocarbon phase comprises asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water, and diluted bitumen (i.e., bitumen and solvent). The hydrocarbon phase continues to consolidate with time, expelling water, in particular from the asphaltene flocs.
As water is expelled, the hydrocarbon phase settles and becomes increasingly viscous until it is no longer fluid and cannot be easily pumped. The rheology of the settled layer is significantly transformed over time from a Newtonian-like slurry to a Bingham-type plastic with a measurable yield stress and ultimately to an intractable solids phase. The lack of fluidity of the settled layer may cause solids to
and a hydrocarbon emulsion comprising water and residual bitumen enriched in asphaltenes. The underflow is withdrawn from the bottom of the primary separation vessel. The underflow is then usually further treated in secondary and subsequent separation vessels to recover residual bitumen.
The underflow from the paraffinic froth treatment process described above may also be treated to form agglomerates of asphaltenes and clays that may then be withdrawn as a separate product stream, as described in Canadian patent No. 2,232,929.
One problem with current conditioning processes is that precipitated asphaltenes in the underflow of bitumen froth separation vessels agglomerate, which agglomerates can form solid masses that can interfere with processing equipment.
For instance, in the paraffinic froth treatment process, the underflow separates over time into a water and hydrocarbon phase. The water phase comprises free water and mineral solids. The hydrocarbon phase comprises asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water, and diluted bitumen (i.e., bitumen and solvent). The hydrocarbon phase continues to consolidate with time, expelling water, in particular from the asphaltene flocs.
As water is expelled, the hydrocarbon phase settles and becomes increasingly viscous until it is no longer fluid and cannot be easily pumped. The rheology of the settled layer is significantly transformed over time from a Newtonian-like slurry to a Bingham-type plastic with a measurable yield stress and ultimately to an intractable solids phase. The lack of fluidity of the settled layer may cause solids to
3 build-up on the froth separation vessel, plug the bottom of the vessel or, because of the size of the agglomerates, damage underflow pumps, all of which may cause transportation problems and potentially stop the process.
Although the dewatering of asphaltene flocs and resultant consolidation of the hydrocarbon phase could arise in any number of processes for recovering bitumen from oil sand, it is of particular concern in the paraffinic froth treatment process.
There is therefore a need in the art for a method or system to inhibit the dewatering of asphaltene flocs in a settled layer near the bottom of a bitumen froth separation vessel, in order that this layer remains fluid for a longer period of time and plugging of the separation vessel is inhibited.
It has surprisingly been determined that addition of a water-asphaltene dispersant can inhibit the dewatering of asphaltene flocs.
SUMMARY OF THE INVENTION
According to one aspect of the present invention, there is provided a system for inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel, into which vessel a diluted bitumen froth is supplied via a froth supply conduit and in which vessel the froth is separated into a low density fraction comprising bitumen and a solvent and a high density fraction comprising solid particles, water and asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water, the system comprising a first injection assembly for injecting a water-asphaltene dispersant and a second injection assembly for injecting the solvent into the conduit, which first injection assembly and
Although the dewatering of asphaltene flocs and resultant consolidation of the hydrocarbon phase could arise in any number of processes for recovering bitumen from oil sand, it is of particular concern in the paraffinic froth treatment process.
There is therefore a need in the art for a method or system to inhibit the dewatering of asphaltene flocs in a settled layer near the bottom of a bitumen froth separation vessel, in order that this layer remains fluid for a longer period of time and plugging of the separation vessel is inhibited.
It has surprisingly been determined that addition of a water-asphaltene dispersant can inhibit the dewatering of asphaltene flocs.
SUMMARY OF THE INVENTION
According to one aspect of the present invention, there is provided a system for inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel, into which vessel a diluted bitumen froth is supplied via a froth supply conduit and in which vessel the froth is separated into a low density fraction comprising bitumen and a solvent and a high density fraction comprising solid particles, water and asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water, the system comprising a first injection assembly for injecting a water-asphaltene dispersant and a second injection assembly for injecting the solvent into the conduit, which first injection assembly and
4 second injection assembly are longitudinally spaced at a distance along the conduit and wherein the first injection assembly is located upstream of the second injection assembly.
According to another aspect of the present invention, there is provided a method of inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel, in which vessel a diluted bitumen froth is separated into a low density fraction comprising bitumen and a solvent and a high density fraction, comprising solid particles, water and asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water, the method comprising adding a water-asphaltene dispersant to the bitumen prior to adding solvent.
According to a further aspect of the present invention, there is provided a method of inhibiting dewatering of asphaltene flocs comprising adding a water-asphaltene dispersant.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a system for the addition of a water-asphaltene dispersant in a paraffinic froth treatment process according to one embodiment of the invention.
DETAILED DESCRIPTION
Asphaltenes are organic components in heavy oil largely comprising fused aromatic rings, which generally also contain nitrogen, sulfur and oxygen molecules. The asphaltene fraction of oil is typically defined as the fraction that is not soluble in linear alkanes, such as n-pentane or n-heptane, or paraffins, but is soluble in toluene or benzene.
Asphaltenes are typically dispersed in oil. When asphaltenes precipitate out of solution, such as on the addition of a paraffinic solvent, they agglomerate, forming a settled layer at the bottom of a bitumen froth separation
According to another aspect of the present invention, there is provided a method of inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel, in which vessel a diluted bitumen froth is separated into a low density fraction comprising bitumen and a solvent and a high density fraction, comprising solid particles, water and asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water, the method comprising adding a water-asphaltene dispersant to the bitumen prior to adding solvent.
According to a further aspect of the present invention, there is provided a method of inhibiting dewatering of asphaltene flocs comprising adding a water-asphaltene dispersant.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a system for the addition of a water-asphaltene dispersant in a paraffinic froth treatment process according to one embodiment of the invention.
DETAILED DESCRIPTION
Asphaltenes are organic components in heavy oil largely comprising fused aromatic rings, which generally also contain nitrogen, sulfur and oxygen molecules. The asphaltene fraction of oil is typically defined as the fraction that is not soluble in linear alkanes, such as n-pentane or n-heptane, or paraffins, but is soluble in toluene or benzene.
Asphaltenes are typically dispersed in oil. When asphaltenes precipitate out of solution, such as on the addition of a paraffinic solvent, they agglomerate, forming a settled layer at the bottom of a bitumen froth separation
5 vessel.
Analysis of the composition of the settled layer from a primary bitumen froth separation vessel, and produced according to the process described in Canadian patent No. 2,232,929, has indicated that asphaltenes are present in this layer as flocs containing emulsified water of particle size less than 10 microns, and ultrafine solids which are less than 2 microns in size.
As discussed above, the flocs in the settled layer gradually expel emulsified water. The rate of expulsion is dependent on a number of factors, such as residence time in the separation vessel and shear forces arising from mixing the settled layer during the treatment process. As a result of these factors, emulsified water droplets grow in the flocs until eventually separating into the water phase.
It was surprisingly found that addition of a water-asphaltene dispersant significantly changed the theology of the settled layer, by improving its fluidity as measured by a reduction in yield stress. Particularly preferred water-asphaltene dispersants reduce the yield stress by about 50~.
In the method and system of the present invention, water-asphaltene dispersants include organic polymers that adhere to both water and asphaltenes. Suitable dispersants comprise a hydrophilic portion and a hydrophobic portion.
Preferably the polymer used in the method and system of the present invention is a hydrophilic organic polymer.
Analysis of the composition of the settled layer from a primary bitumen froth separation vessel, and produced according to the process described in Canadian patent No. 2,232,929, has indicated that asphaltenes are present in this layer as flocs containing emulsified water of particle size less than 10 microns, and ultrafine solids which are less than 2 microns in size.
As discussed above, the flocs in the settled layer gradually expel emulsified water. The rate of expulsion is dependent on a number of factors, such as residence time in the separation vessel and shear forces arising from mixing the settled layer during the treatment process. As a result of these factors, emulsified water droplets grow in the flocs until eventually separating into the water phase.
It was surprisingly found that addition of a water-asphaltene dispersant significantly changed the theology of the settled layer, by improving its fluidity as measured by a reduction in yield stress. Particularly preferred water-asphaltene dispersants reduce the yield stress by about 50~.
In the method and system of the present invention, water-asphaltene dispersants include organic polymers that adhere to both water and asphaltenes. Suitable dispersants comprise a hydrophilic portion and a hydrophobic portion.
Preferably the polymer used in the method and system of the present invention is a hydrophilic organic polymer.
6 Preferred are non-ionic or anionic hydrophilic organic polymers, especially those having a polar non-ionic or anionic hydrophilic portion and a long hydrocarbon or fatty chain hydrophobic portion.
Preferred are water-asphaltene dispersants having an intermediate to high hydrophile-lipophile balance (HLB).
HLB is essentially the measure of the type of surfactant properties a comgound may have; i.e., water-in-oil emulsifier (low) vs. solubilizing agent (high) vs. oil-in-water emulsifier (intermediate to high). However, HLB is not the only factor that determines suitability of a compound as a water-asphaltene dispersant. Other factors, such as the type of polymer backbone, are also important.
Exemplary polymer backbones may be selected from hydrophobic base resins such as fatty resins, especially a fatty acid (e. g., a tall oil resin) or fatty amine; aromatic resins; polypropylene oxides; or polyalphaolefins. The hydrophobic portion may be punctuated with heteroatoms, or be sulphonated. Hydrophilic resins may also be used as the backbone, such as polyethylene oxides, provided that the appropriate polar functionality is present.
Preferably the organic polymer used in the present invention has multiple ethylene oxide (hydrophilic) and propylene oxide (hydrophobic) branches.
Particularly preferred is a water-asphaltene dispersant having ethylene oxide end groups, with propylene oxide, polypropylene oxide or cross-linked polypropylene oxide moieties in between the end groups.
Where a sulphonated polymer is used, preferably the hydrophobic portion comprises a sulphonate, such as an alkylarylsulphonate.
Preferred are water-asphaltene dispersants having an intermediate to high hydrophile-lipophile balance (HLB).
HLB is essentially the measure of the type of surfactant properties a comgound may have; i.e., water-in-oil emulsifier (low) vs. solubilizing agent (high) vs. oil-in-water emulsifier (intermediate to high). However, HLB is not the only factor that determines suitability of a compound as a water-asphaltene dispersant. Other factors, such as the type of polymer backbone, are also important.
Exemplary polymer backbones may be selected from hydrophobic base resins such as fatty resins, especially a fatty acid (e. g., a tall oil resin) or fatty amine; aromatic resins; polypropylene oxides; or polyalphaolefins. The hydrophobic portion may be punctuated with heteroatoms, or be sulphonated. Hydrophilic resins may also be used as the backbone, such as polyethylene oxides, provided that the appropriate polar functionality is present.
Preferably the organic polymer used in the present invention has multiple ethylene oxide (hydrophilic) and propylene oxide (hydrophobic) branches.
Particularly preferred is a water-asphaltene dispersant having ethylene oxide end groups, with propylene oxide, polypropylene oxide or cross-linked polypropylene oxide moieties in between the end groups.
Where a sulphonated polymer is used, preferably the hydrophobic portion comprises a sulphonate, such as an alkylarylsulphonate.
7 Dispersants useful in the system and method of the invention will generally have a molecular weight ranging from 500 to 25000. However, the molecular weight may also fall within the range of 5000 to 15000, or even 2000 to 2500.
In the paraffinic froth treatment process, asphaltenes precipitate out of solution upon the addition of paraffinic solvent. Precipitating asphaltenes come into contact and agglomerate with water droplets and ultrafine solids forming flocs, which are essentially asphaltene coated clusters of asphaltenes, emulsified water and ultrafine solids. In the underflow, the asphaltenes continue to phase separate and, as described above, the flocs consolidate as water is expelled. It is believed that co-precipitated water-asphaltene dispersants collect at the interface of asphaltenes and emulsifed water in the flocs, thereby inhibiting water droplet growth in the flocs that leads to their dewatering.
Moreover, it is believed that while the hydrophilic portion of water-asphaltene dispersants is adsorbed on the asphaltenes, the hydrophobic portion extends beyond the surface of the asphaltenes providing surface structure, which inhibits agglomeration. By inhibiting agglomeration, the fluidity of the settled layer is improved.
Some water-asphaltene dispersants also have cross-linking functionality, such as some fatty polymers. Cross-linking at the surface of the asphaltenes may give rise to a more complex surface structure that could further inhibit agglomeration, or may give rise to film formation that could inhibit water transportation into and out of the asphaltene floc.
In the paraffinic froth treatment process, asphaltenes precipitate out of solution upon the addition of paraffinic solvent. Precipitating asphaltenes come into contact and agglomerate with water droplets and ultrafine solids forming flocs, which are essentially asphaltene coated clusters of asphaltenes, emulsified water and ultrafine solids. In the underflow, the asphaltenes continue to phase separate and, as described above, the flocs consolidate as water is expelled. It is believed that co-precipitated water-asphaltene dispersants collect at the interface of asphaltenes and emulsifed water in the flocs, thereby inhibiting water droplet growth in the flocs that leads to their dewatering.
Moreover, it is believed that while the hydrophilic portion of water-asphaltene dispersants is adsorbed on the asphaltenes, the hydrophobic portion extends beyond the surface of the asphaltenes providing surface structure, which inhibits agglomeration. By inhibiting agglomeration, the fluidity of the settled layer is improved.
Some water-asphaltene dispersants also have cross-linking functionality, such as some fatty polymers. Cross-linking at the surface of the asphaltenes may give rise to a more complex surface structure that could further inhibit agglomeration, or may give rise to film formation that could inhibit water transportation into and out of the asphaltene floc.
8 A number of commercially available ethylene oxide (EO)/propylene oxide (PO) surfactants were tested for activity as water-asphaltene dispersants having a range of EO/PO of between 0.1 and 1Ø
To test the ability of these agents to act as water-asphaltene dispersants, a test sample was taken from the underflow of a primary separation vessel in a paraffinic froth flotation process, such as described in Canadian patent No. 2,149,737. The sample was then mixed at varying rates, thereby subjecting the sample to different shear. A
number of tests were run in which mixing speed, mixing time and rest time were systematically varied to simulate the process.
A water-asphaltene dispersant was one in which the asphaltenes in the sample did not consolidate to an intractable mass at the end of a run. Particularly preferred were those dispersants in which the sample remained fluid throughout a run. PA0256, commercially available from Baker Petrolite, was found to be a suitable water-asphaltene dispersant.
The amount of water-asphaltene dispersant used in the method and system of the invention will vary. Preferred amounts may be determined by a person skilled in the art through routine experimentation. Typical amounts range from 50 to 1250 ppmw, based on the total weight of the froth, added in single or divided doses. Most preferably the water-asphaltene dispersant is added in two doses. The same amount need not be added in each dose. If too much of the dispersant is added at one time, the floc may be overtreated, which could adversely affect settling rates of the heavy fraction from the light fraction in the bitumen froth separation vessel. If too little is added there may
To test the ability of these agents to act as water-asphaltene dispersants, a test sample was taken from the underflow of a primary separation vessel in a paraffinic froth flotation process, such as described in Canadian patent No. 2,149,737. The sample was then mixed at varying rates, thereby subjecting the sample to different shear. A
number of tests were run in which mixing speed, mixing time and rest time were systematically varied to simulate the process.
A water-asphaltene dispersant was one in which the asphaltenes in the sample did not consolidate to an intractable mass at the end of a run. Particularly preferred were those dispersants in which the sample remained fluid throughout a run. PA0256, commercially available from Baker Petrolite, was found to be a suitable water-asphaltene dispersant.
The amount of water-asphaltene dispersant used in the method and system of the invention will vary. Preferred amounts may be determined by a person skilled in the art through routine experimentation. Typical amounts range from 50 to 1250 ppmw, based on the total weight of the froth, added in single or divided doses. Most preferably the water-asphaltene dispersant is added in two doses. The same amount need not be added in each dose. If too much of the dispersant is added at one time, the floc may be overtreated, which could adversely affect settling rates of the heavy fraction from the light fraction in the bitumen froth separation vessel. If too little is added there may
9 be no effect. It was found that the most preferred amount for agents tested was 200 to 600 ppmw.
The type and amount of water-asphaltene dispersant must be selected keeping in mind the potential interference with upstream and downstream processes. For instance, in addition to taking care to avoid a detrimental effect on froth treatment settling rates, the agent and amount should be chosen to avoid inhibiting bitumen extraction, the action of hydroprocessing catalysts, and the effect of anti-foaming agents.
The effectiveness of a water-asphaltene dispersant may decrease with time. For instance, it was discovered that a settled phase that was treated with a water-asphaltene dispersant and left to stand for 24 hours without mixing, still compacted and dewatered. Therefore, it may not be possible to maintain the viscosity of the settled phase indefinitely upon addition of a water-asphaltene dispersant.
Figure 1 shows a system for the addition of a water-asphaltene dispersant to a paraffinic froth treatment process. A bitumen froth (10) is delivered into a storage tank (20) and transported to a primary separation vessel (30) via a froth supply conduit (35) . In the supply conduit, paraffinic solvent is added (40), as well as a water-asphaltene dispersant (50). The overflow from the primary separation vessel is removed (60). The overflow is treated with steam (70) to separate in a further separation vessel (80) bitumen, which is then transferred to an upgrader (90), and solvent, which is recycled (100). The underflow from the primary separation vessel is removed to a secondary separation vessel (110), and again treated with paraffinic solvent. The overflow is removed (120) and recycled to the primary separation vessel. The underflow from the secondary separation vessel is removed to a tertiary separation vessel (130) and again treated with paraffinic solvent (140). The overflow from the tertiary 5 separation vessel is recycled to the secondary separation vessel (150), and the underflow from the tertiary separation vessel is separated by successive steam distillations (160, 170) into tailings (180, 190) and solvent (200, 210) fractions. The solvent fractions are recycled (220, 230).
The type and amount of water-asphaltene dispersant must be selected keeping in mind the potential interference with upstream and downstream processes. For instance, in addition to taking care to avoid a detrimental effect on froth treatment settling rates, the agent and amount should be chosen to avoid inhibiting bitumen extraction, the action of hydroprocessing catalysts, and the effect of anti-foaming agents.
The effectiveness of a water-asphaltene dispersant may decrease with time. For instance, it was discovered that a settled phase that was treated with a water-asphaltene dispersant and left to stand for 24 hours without mixing, still compacted and dewatered. Therefore, it may not be possible to maintain the viscosity of the settled phase indefinitely upon addition of a water-asphaltene dispersant.
Figure 1 shows a system for the addition of a water-asphaltene dispersant to a paraffinic froth treatment process. A bitumen froth (10) is delivered into a storage tank (20) and transported to a primary separation vessel (30) via a froth supply conduit (35) . In the supply conduit, paraffinic solvent is added (40), as well as a water-asphaltene dispersant (50). The overflow from the primary separation vessel is removed (60). The overflow is treated with steam (70) to separate in a further separation vessel (80) bitumen, which is then transferred to an upgrader (90), and solvent, which is recycled (100). The underflow from the primary separation vessel is removed to a secondary separation vessel (110), and again treated with paraffinic solvent. The overflow is removed (120) and recycled to the primary separation vessel. The underflow from the secondary separation vessel is removed to a tertiary separation vessel (130) and again treated with paraffinic solvent (140). The overflow from the tertiary 5 separation vessel is recycled to the secondary separation vessel (150), and the underflow from the tertiary separation vessel is separated by successive steam distillations (160, 170) into tailings (180, 190) and solvent (200, 210) fractions. The solvent fractions are recycled (220, 230).
10 The tailings are delivered to a tailings settling pond (240) .
The froth supply conduit (35) comprises a water-asphaltene dispersant injection assembly, which may comprise one or more water-asphaltene dispersant injection orifices, and a solvent injection assembly, which may comprise one or more solvent injection orifices. The distance between any of the water-asphaltene dispersant injection orifices and any of the solvent injection orifices should be sufficient to facilitate complete mixing with the bitumen froth, taking into account the density and viscosity differences between the froth and the water-asphaltene dispersant.
In the paraffinic froth treatment process, injection of the water-asphaltene dispersant into the froth supply conduit should be upstream of the points) where solvent is injected into the conduit. This will facilitate co-precipitation of the water-asphaltene dispersant with the asphaltenes on addition of the paraffinic solvent. Water-asphaltene dispersants may comprise organic polymers that are incompatible with the solvent, such that if the dispersant is introduced into the paraffinic solvent first, a substantial amount of the water-asphaltene dispersant could precipitate and be rendered ineffective.
The froth supply conduit (35) comprises a water-asphaltene dispersant injection assembly, which may comprise one or more water-asphaltene dispersant injection orifices, and a solvent injection assembly, which may comprise one or more solvent injection orifices. The distance between any of the water-asphaltene dispersant injection orifices and any of the solvent injection orifices should be sufficient to facilitate complete mixing with the bitumen froth, taking into account the density and viscosity differences between the froth and the water-asphaltene dispersant.
In the paraffinic froth treatment process, injection of the water-asphaltene dispersant into the froth supply conduit should be upstream of the points) where solvent is injected into the conduit. This will facilitate co-precipitation of the water-asphaltene dispersant with the asphaltenes on addition of the paraffinic solvent. Water-asphaltene dispersants may comprise organic polymers that are incompatible with the solvent, such that if the dispersant is introduced into the paraffinic solvent first, a substantial amount of the water-asphaltene dispersant could precipitate and be rendered ineffective.
11 Preferably the water-asphaltene dispersant is introduced into the system via an aromatic carrier, such as a naphtha or naphtha/gas oil carrier.
A suitable water-asphaltene dispersant may also be used as a post-conditioning treatment to break up asphaltene agglomerates. Addition of a water-asphaltene dispersant to a solidified underflow could soften the underflow, with or without mixing. The length of time the water-asphaltene dispersants would need to be in contact with the solidified underflow may be determined through routine experimentation.
Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is readily apparent to those of ordinary skill in the art in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the appended claims.
The citation of any publication, patent or patent application in this specification is not an admission that the publication, patent or patent application is prior art.
It must be noted that as used in the specification and the appended claims, the singular forms of "a", "an" and "the" include plural reference unless the context clearly indicates otherwise.
Unless defined otherwise all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs.
A suitable water-asphaltene dispersant may also be used as a post-conditioning treatment to break up asphaltene agglomerates. Addition of a water-asphaltene dispersant to a solidified underflow could soften the underflow, with or without mixing. The length of time the water-asphaltene dispersants would need to be in contact with the solidified underflow may be determined through routine experimentation.
Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is readily apparent to those of ordinary skill in the art in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the appended claims.
The citation of any publication, patent or patent application in this specification is not an admission that the publication, patent or patent application is prior art.
It must be noted that as used in the specification and the appended claims, the singular forms of "a", "an" and "the" include plural reference unless the context clearly indicates otherwise.
Unless defined otherwise all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs.
Claims (17)
1. A system for inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel, into which vessel a diluted bitumen froth is supplied via a froth supply conduit and in which vessel the froth is separated into a low density fraction comprising bitumen and a solvent and a high density fraction comprising solid particles, water and asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water, the system comprising a first injection assembly for injecting a water-asphaltene dispersant and a second injection assembly for injecting the solvent into the conduit, which first injection assembly and second injection assembly are longitudinally spaced at a distance along the conduit and wherein the first injection assembly is located upstream of the second injection assembly.
2. The system of claim 1, wherein the distance between the first injection assembly and the second injection assembly facilitates complete mixing of the froth and the water-asphaltene dispersant and the froth and the solvent.
3. The system of claim 1 or 2, wherein the first injection assembly comprises one or more water-asphaltene dispersant injection orifices and the second injection assembly comprises one or more solvent injection orifices.
4. The system of claim 1, 2 or 3, wherein the solvent is a paraffinic solvent.
5. The system of claim 1, 2, 3 or 4, wherein the water-asphaltene dispersant is added in an amount of 50 to 1250 ppmw, based on the total weight of the froth.
6. The system of claim 1, 2, 3 or 4, wherein the water-asphaltene dispersant is added in an amount of 200 to 600 ppmw, based on the total weight of the froth.
7. A method of inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel, in which vessel a diluted bitumen froth is separated into a low density fraction comprising bitumen and a solvent and a high density fraction, comprising solid particles, water and asphaltene flocs, which flocs comprise an emulsion of asphaltenes and water, the method comprising adding a water-asphaltene dispersant to the bitumen prior to adding solvent.
8. The method of claim 7, wherein the solvent is a paraffinic solvent.
9. The method of claim 7 or 8, wherein the water-asphaltene dispersant is added in an amount of 50 to 1250 ppmw, based on the total weight of the froth.
10. The method of claim 7 or 8, wherein the water-asphaltene dispersant is added in an amount of 200 to 600 ppmw, based on the total weight of the froth.
11. The method of claim 7, 8, 9 or 10, wherein the water-asphaltene dispersant is added in a single or divided dose.
12. The method of claim 7, 8, 9, 10 or 11, wherein the froth is supplied to the bitumen froth separation vessel via a froth supply conduit and the water-asphaltene dispersant is injected into the froth supply conduit at a location upstream of a point where solvent is injected into the conduit.
13. A method of inhibiting dewatering of asphaltene flocs comprising adding a water-asphaltene dispersant.
14. The method of claim 13, wherein the water-asphaltene dispersant is a hydrophilic organic polymer.
15. The method of claim 14, wherein the hydrophilic organic polymer is a long chain polymer with multiple ethylene oxide and propylene oxide branches.
16. The method of claim 15, wherein the hydrophilic organic polymer has an EO/PO of between 0.1 and 1Ø
17. The method of claim 14, 15 or 16, wherein the hydrophilic organic polymer has a molecular weight of 500 to 25000.
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| CA2502329A CA2502329C (en) | 2005-03-24 | 2005-03-24 | Method and system for inhibiting dewatering of asphaltene flocs in a bitumen froth separation vessel |
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